Silicone polymer diol compositions and condensation polymer/silicone polymer blends

ABSTRACT

The invention herein provides a silicone polymer emulsion comprising: a) a silicone polymer; and b) a surfactant; and a liquid continuous phase comprising a diol, wherein the diol comprises from about 25 to about 100% by weight of the continuous phase. Further provided is a method of making a condensation polymer/ silicone polymer blend comprising the steps of: a) preparing a silicone polymer emulsion comprising a silicone polymer in a liquid continuous phase; b) introducing the silicone polymer emulsion into a condensation polymerization reaction medium prior to or during the condensation polymerization reaction, wherein the condensation polymerization reaction medium comprises (1) a diacid, di-isocyanate, dialkyl carbonate, diaryl carbonate, dihalo carbonate or a mixture thereof, wherein the continuous phase, the condensation polymerization reaction medium or both comprises a diol component; and c) polymerizing the diol and component b(1) thereby forming a condensation polymer/silicone polymer blend. Polymer blends comprising a condensation polymer/silicone polymer blend are also provided.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a divisional of, and claims the benefit of,application Ser. No. 09/518,071, filed on Mar. 2, 2000, which status isallowed. The 09/518,071 application claims priority to U.S. ProvisionalApplication Serial No. 60/122,625, filed Mar. 3, 1999. U.S. applicationSer. Nos. 09/518,071 and 60/122,625 are each incorporated herein by thisreference in their entireties.

FIELD OF THE INVENTION

[0002] This application relates to silicone polymer diol emulsions. Thisapplication further relates to silicone blend condensation polymers andmethods of making the same. Such condensation polymers may be preparedby introducing a silicone polymer emulsion into a condensationpolymerization reaction to provide a condensation polymer/siliconepolymer blend. The silicone polymer emulsions utilized in thepreparation of the condensation polymers may comprise water, diol and,optionally cosolvents.

BACKGROUND

[0003] It is known to modify condensation polymers by blending thecondensation polymer with another polymer in an extruder. For example,to improve the impact properties of a polyester, a low Tg elastomer istypically added to the polyester in a twin-screw extruder. Japan KokaiJP 02155944 describes compounds for molded articles comprising physicalblends of saturated polyester with polystyrene polymers containing 1-100phr glycidylamido-grafted olefin polymers of glycidylmethacrylateAttorney graft olefin polymers. The size of the dispersedphase is critical in obtaining good properties. However, such extrusionprocesses are energy intensive, and often result in the reduction in thephysical properties of the polymer, in particular the molecular weight,and require a blending step, which utilizes more resources and moretime.

[0004] Typically, low Tg elastomers are used to impact modify thepolyester. These low Tg elastomers are difficult to handle and oftenrequire that a second monomer, such as poly(methyl methacrylate) to beutilized as a “shell” surrounding the low Tg polymer “core” so that thelow Tg polymer may be handled. The core-shell polymer is isolated, driedand then added to the polyester in an extruder. U.S. Pat. Nos.5,652,306, 4,180,494 and 5,409,967 disclose compositions for impactmodification of aromatic polyesters that involve blending an acrylic orpolybutadiene/acrylic rubber powder with polylethylene terephthalate(PET). The acrylic rubber particles are prepared by typical core/shellemulsion polymerization and then harvested by spray drying the emulsion.The harvested rubber is then melt blended in an extruder to produce theimpact modified PET.

[0005] Silicone rubber has also been utilized as a low Tg polymer formodifiying polyesters. U.S. Pat. No. 5,594,059 discusses the melt mixingof silicone rubber powder into polyester and polycarbonate blends. Thesecompositions are a physical blend of silicone rubber andpolyester/polycarbonates. As noted, such melt mixing techniques areexpensive and time consuming, thus, it would be beneficial to be able tocombine silicone polymers with materials such as polyesters without theneed for such mixing.

[0006] There exists a need for a process for producing a polymer blendby more economical methods. Such a need has been solved by the presentinvention, which can achieve such a blend in a polymerization reactor,wherein the physical properties of the condensation polymer aremaintained or improved.

SUMMARY OF THE INVENTION

[0007] In one aspect, the invention provides a silicone polymer emulsioncomprising:

[0008] a. a silicone polymer;

[0009] b. a surfactant; and

[0010] c. a liquid continuous phase comprising a diol, wherein the diolcomprises from about 25 to about 100% by weight of the continuous phase.

[0011] In a further aspect, the invention provides a method of making acondensation polymer/ silicone polymer blend comprising the steps of:

[0012] a. preparing a silicone polymer emulsion comprising a siliconepolymer in a liquid continuous phase;

[0013] b. introducing the silicone polymer emulsion into a condensationpolymerization reaction medium prior to or during the condensationpolymerization reaction, wherein the condensation polymerizationreaction medium comprises (1) a diacid, di-isocyanate; dialkylcarbonate, diaryl carbonate, dihalo carbonate or a mixture thereof, andwherein the continuous phase, the condensation polymerization reactionmedium or both comprises a diol component; and

[0014] c. polymerizing the diol and component b(1), thereby forming acondensation polymer/silicone polymer blend.

[0015] In yet a further aspect, the invention provides a method ofmaking a condensation polymer/silicone polymer blend comprising thesteps of:

[0016] a. preparing a polymer colloid system comprising a siliconepolymer dispersed in a liquid continuous phase;

[0017] b. introducing the polymer colloid system into a glycolysisreaction medium prior to or during the glycolysis reaction wherein theglycolysis reaction medium comprises a polyester, copolyester,polyesteramide, polycarbonate, or a mixture thereof, wherein the liquidcontinuous phase, the gylcolysis reaction medium, or both comprises adiol component;

[0018] and

[0019] c. polymerizing the fully or partially glycolyzed polyester,copolyester, polyesteramide, polycarbonate or mixture thereof, therebyproviding a condensation polymer/silicone polymer blend.

[0020] In yet a further embodiment, the invention provides a method ofmaking a condensation polymer/ silicone polymer blends comprising thesteps of:

[0021] a. preparing a polymer colloid system comprising a siliconepolymer and a liquid continuous phase;

[0022] b. introducing the polymer colloid system into a condensationpolymer;

[0023] and

[0024] c. extruding the polymer colloid system and the condensationpolymer, thereby providing a condensation polymer/ silicone polymerblend.

[0025] Additional advantages of the invention will be set forth in partin the description which follows, and in part will be apparent from thedescription, or may be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combinations particularly pointed out in the appendedclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the invention, as claimed.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The present invention may be understood more readily by referenceto the following detailed description of preferred embodiments of theinvention and the Examples included therein.

[0027] Before the present compositions of matter and methods aredisclosed and described, it is to be understood that this invention isnot limited to specific synthetic methods or to particular formulations,and, as such, may, of course, vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting.

[0028] In this specification and in the claims which follow, referencewill be made to a number of terms which shall be defined to have thefollowing meanings.

[0029] The singular forms a, an and the include plural referents unlessthe context clearly dictates otherwise.

[0030] Optional or optionally means that the subsequently describedevent or circumstances may or may not occur, and that the descriptionincluded instances where said event or circumstance occurs and instanceswhere it does not.

[0031] Silicone polymer emulsion is herein defined as a dispersion ofpolymeric particles in a continuous phase, the polymeric particlespreferably having a size range of from about 0.1 to about 10 microns.The silicone polymers of the present invention preferably have amolecular weight of from about 5,000 to about 1,000,000 Daltons. Thepolymeric particles are preferably produced through emulsionpolymerization processes. Alternatively, such emulsions may be preparedthrough direct emulsification e.g., mechanical emulsification processes.

[0032] Ranges are often expressed herein as from about one particularvalue, and/or to about another particular value. When such a range isexpressed, it is to be understood that another embodiment is from theone particular value and/or to the other particular value. Similarly,when values are expressed as approximations, by use of the antecedent“about,” it will be understood that the particular value is anotherembodiment.

[0033] Diol is a synonym for glycol or dihydric alcohol. Polyol is apolyhydric alcohol containing three or more hydroxyl groups.

[0034] The abbreviation “run” means nanometers. “Tg” means glasstransition temperature.

[0035] As used herein, the term “condensation polymerization” is used torefer to condensation polymerization reactions and “condensationpolymer” is the product thereof. The term “condensation polymerization”as used herein is also used to refer more generally to polymerizationreactions of the step-growth-type. As used herein, the term“condensation polymer” is synonymous with “step-growth polymer.”

[0036] Throughout this application, where publications are referenced,the disclosures of these publications in their entireties are herebyincorporated by reference into this application in order to more fullydescribe the state of the art to which this invention pertains.

[0037] In one aspect, the invention provides a silicone polymer emulsioncomprising:

[0038] a. a silicone polymer;

[0039] b. a surfactant; and

[0040] d. a liquid continuous phase comprising a diol, wherein the diolcomprises from about 25 to about 100% by weight of the continuous phase.

[0041] In a further aspect, the invention provides a method of making acondensation polymer/silicone polymer blend comprising the steps of:

[0042] a. preparing a silicone polymer emulsion comprising a siliconepolymer in a liquid continuous phase;

[0043] b. introducing the silicone polymer emulsion into a condensationpolymerization reaction medium prior to or during the condensationpolymerization reaction;

[0044] wherein the condensation polymerization reaction medium comprises(1) a diacid, di-isocyanate; dialkyl carbonate, diaryl carbonate, dihalocarbonate or a mixture thereof,

[0045] and wherein the continuous phase, the condensation polymerizationreaction medium or both comprises a diol component; and

[0046] c. polymerizing the diol and component b(1) thereby forming acondensation polymer/silicone polymer blend.

[0047] In yet a further aspect, the invention provides a method ofmaking a condensation polymer/silicone polymer blend comprising thesteps of:

[0048] a. preparing a polymer colloid system comprising a siliconepolymer dispersed in a liquid continuous phase;

[0049] b. introducing the polymer colloid system into a glycolysisreaction medium prior to or during the glycolysis reaction wherein theglycolysis reaction medium comprises a polyester, copolyester,polyesteramide, polycarbonate or a mixture thereof;

[0050] wherein the liquid continuous phase, the gylcolysis reactionmedium, or both comprises a diol component; and

[0051] c. polymerizing the fully or partially glycolyzed polyester,copolyester, polyesteramide, polycarbonate or mixture thereof, therebyproviding a condensation polymer/silicone polymer blend.

[0052] In yet a further embodiment, the invention provides a method ofmaking a condensation polymer/ silicone polymer blends comprising thesteps of:

[0053] a. preparing a polymer colloid system comprising a siliconepolymer and a liquid continuous phase;

[0054] b. introducing the polymer colloid system into a condensationpolymer;

[0055] and

[0056] c. extruding the polymer colloid system and the condensationpolymer, thereby providing a condensation polymer/ silicone polymerblend.

[0057] Still further, the invention provides products made by theprocesses herein.

[0058] I. Silicone Polymer Emulsion

[0059] In one embodiment, the aqueous silicone polymer emulsions of thepresent invention comprise a plurality of silicone polymer particles.The silicone polymers of the present invention may preferably havefunctional groups. Such functional groups may comprise amino, epoxy,vinyl, mercapto, carbonate, isocyanate or silicone hydride. In aparticularly preferred embodiment, the silicone polymer is silanolterminated polydiorganosiloxane (“PDOS”). Other preferred siliconepolymers include alkylmethylsiloxanes or aminopropylsiloxanes.

[0060] The silicone polymer emulsion preferably contains at least onesurfactant that stabilizes the dispersed silicone polymer particles inthe emulsion. The emulsion should preferably have an average particlesize from about 0.1 to about 10 microns. Such emulsions may be prepared,for example, by methods wherein a cyclic or linear oligomeric siliconepolymer, such as PDOS, is dispersed in an aqueous continuous phase withthe aid of the above mentioned surfactant and are thereafter emulsionpolymerized by the introduction of an acid or base catalyst. Theseemulsions can be illustrated by the disclosures of, among others, U.S.Pat. Nos. 4,954,565, 4,618,642, 3,294,725, and 2,891,920, each of whichare hereby incorporated herein in their entireties by this reference.

[0061] In a preferred embodiment, the silicone polymer emulsions areprepared by a direct emulsification process. In this process, a mixtureof water, and/or diol silicone polymer and one or more surfactants areprocessed under high shear conditions using either conventional mixingequipment or high shear devices such as a Microfuidizer™. Methods forpreparing these polymer emulsions are given in U.S. Pat. Nos. 4,177,177and 4,788,001, each of which are herein incorporated in their entiretiesby this reference. When water is present in the silicone polymeremulsions, water is present from about 10 to about 70% by weight, and,more preferably, about 10 to about 50% by weight.

[0062] In still a further embodiment, the continuous phase comprises awater component, wherein the water component is present in an amount offrom about 1 to about 25% by weight, based upon the total weight of thecontinuous phase, and further preferably, about 1 to about 50% byweight, based upon the total weight of the continuous phase, and stillpreferably, from about 1 to about 75% by weight, based upon the totalweight of the continuous phase.

[0063] In a further, still preferred embodiment, the silicone polymeremulsions of this present invention comprise a diol. Diol componentsuseful for the continuous phase of the diol silicone polymer emulsioncompositions include, but are not limited to, any aliphatic orcycloaliphatic diol having from about 2 to about 10 carbon atoms, or amixture thereof. Preferred diols include ethylene diol, 1,3-trimethylenediol, propylene diol, tripropylene diol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol,1,9-nonanediol, neopentyl diol, cis- or trans-cyclohexanedimethanol,cis- or trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, diethylenediol,2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propanediol,2-methyl-1,3-pentanediol, or a mixture thereof, more preferred diolsinclude ethylene diol, propylene diol, tripropylene diol,1,4-butanediol, diethylene diol, neopentyl diol, cis and trans-cyclohexanedimethanol, or a mixture thereof; even more preferred diolsinclude neopentyl diol, ethylene diol, cis or transcyclohexanedimethanol, 1,4 butanediol, or a mixture thereof.

[0064] In one embodiment, the diol component is present in an amount offrom about 25 to about 100% by weight, based on the total weight of thecontinuous phase, preferably from about 30 to about 100% by weight,based on the total weight of the continuous phase, more preferably, fromabout 40 to about 100% by weight, based on the total weight of thecontinuous phase, more preferably, from about 50 to about 100% byweight, based on the total weight of the continuous phase, and, evenmore preferably, about 60 to about 100% by weight, based on the totalweight of this continuous phase. In a further embodiment, the diolcomprises from about 70 to about 100% by weight of the continuous phase,in a further embodiment, about 80 to about 100% by weight of thecontinuous phase, and in still a further embodiment, about 90 to about100% by weight ofthe continuous phase. In a further embodiment, the diolcontaining phase consists essentially of the diol component. In afurther embodiment, the diol is present from about 1 to about 25 percentby weight of the continuous phase. In yet a further embodiment, the diolis present from about 1 to about 100% by weight of the continuous phase.

[0065] The total weight of the continuous phase includes the weight ofthe diol component, water component, polyol component and anyco-solvent. As noted, the weight of any surfactant is not included inthe total weight of the continuous phase. In a preferred embodiment, thediol component consists essentially of tripropylene glycol,1,4-butanediol, neopentyl glycol, cyclohexanedimethanol, or a mixturethereof.

[0066] In a preferred embodiment, a surfactant is present in thesilicone polymer emulsions. A surfactant is preferably used to preparethe silicone polymer emulsions. One of skill in the art would recognizethat the type and amount of surfactant used in the emulsionpolymerization depends on the monomer combinations and thepolymerization conditions. Surfactants used in the emulsionpolymerization may be anionic, cationic, or nonionic. Anionicsurfactants that may be used in the invention include surfactants suchas alkali metal or ammonium salts of alkyl, aryl or alkylarylsulfonates, sulfates, phosphates, or a mixture thereof. Further,suitable nonionic surfactants include, but are not limited to, alkyl andalkylaryl polydiol ethers, such as ethoxylation products of lauryl,oleyl and stearyl alcohols; alkyl phenol glycol ethers, including butnot limited to, ethoxylation products of octyl or nonylphenol. Suitablesurfactants may be found in McCutcheon's Volume I. Emulsifiers andDetergents 1996 North American Edition, MC Publishing Co., Glen Rock,N.J., 1996.

[0067] In addition to the diol component and/or water component, thecontinuous phase may contain one or more polyol components.Representative polyol components that may be used in the continuousphase include, but are not limited to, glycerol, trimethylolpropane,pentaerythritol, 1,2,6-hexanetriol, sorbitol,1,1,4,4-tetrakis(hydroxymethyl)cyclohexane,tris-(2,hydroxyethyl)isocyanurate, dipentaerythritol or a mixturethereof. In addition to low molecular weight polyols, higher molecularweight polyols (MW about 400 to about 3000), preferably triols derivedby condensing alkylene oxides having from about 2 to about 3 carbons,e.g., ethylene oxide or propylene oxide, with polyol initiators, havingfrom about 3 to about 6 carbons, e.g., glycerol, can also be used.

[0068] The continuous phase may also comprise a cosolvent. Thesecosolvents include, but are not limited to water, methanol, ethanol,propanol, n-butanol, or a mixture thereof. The cosolvent may be presentin the amount of less than about 60% by weight, more preferably lessthan about 40% by weight, based on the total weight of the continuousphase.

[0069] Preferably, the silicone polymers utilized to form the emulsionsof the present invention may be crosslinked prior to addition of theemulsion to a condensation polymerization reaction. Many methods arepresent in the literature to crosslink silicone polymer emulsions. Forexample, U.S. Pat. No. 4,370,160 discloses microparticles, such asmicro-spheres and microcapsules, comprising a solid PDOS prepared byirradiation of a dispersion of discrete particles with ultravioletlight. The discrete particles are dispersed in a U.V. transparent fluidcontinuous phase and are sphere-like particles of a U.V. curable, liquidPDOS component containing a material to be encapsulated.

[0070] In another example, U.S. Pat. No. 4,618,642 discloses how tocrosslink aqueous emulsions of silicone particles. The crosslinking iscarried out by mixing an anionic emulsion containing dispersed particlesof hydroxyl functional PDOS, a dialkyltindicarboxylate and atrifunctional organosilane. U.S. Pat. No. 5,674,937, also disclosesmethods of curing phase inverted silicone polymer emulsions.

[0071] The diol silicone emulsions of the present invention may also beprepared by emulsion polymerization techniques. Such emulsions may beprepared, for example, by methods wherein a cyclic or linear oligomersiloxane polymer, such as PDOS, are dispersed in a glycol continuousphase with the aid of a surfactant and are thereafter emulsionpolymerized by the introduction of an acid or base catalyst. Examples ofsuitable acid and base catalysts can be illustrated by the disclosuresof, among others, U.S. Pat. Nos. 4,954,595, 4,618,642, 3,294,725 and2,891,920.

[0072] In a preferred embodiment, the silicone polymer emulsions areprepared by a direct emulsification. In this process, a mixture of diol,silicone polymer and one or more surfactants are processed under highshear conditions using either conventional mixing equipment or highshear device such as a MicroFluidizer™. For example, PDOS can be addedto a surfactant and then the diol slowly added with constant shear untilthe system inverts from a water-in-oil emulsion to an oil-in-wateremulsion. The resulting PDOS emulsions can then be crosslinked usingcommon methods known to crosslink the PDOS.

[0073] II. Condensation Polymerization

[0074] As noted above, the silicone polymer emulsion to be introducedinto the condensation polymerization reaction, may be comprised ofwater, diol, polyol, and mixtures thereof, as well as cosolvents. In aparticularly preferred embodiment, the continuous phase may include atleast some diol, and may also preferably be comprised primarily of diol,so that the diols in the continuous phase of the silicone polymeremulsion may participate in the condensation polymerization reaction.Further, the continuous phase of each silicone polymer emulsion mayconsist essentially of or consist of either water, diol, or polyol, ormay comprise any proportion of any of these components.

[0075] When the polymer colloid system is a silicone polymer emulsionhaving a diol in the continuous phase, the diols in the continuous phaseco-react with the diacids, diisocyanates, dialkyl or diaryl or dihalocarbonates, or mixtures thereof, that comprise the reaction medium whichforms the condensation polymer. In one embodiment, the diol component ispresent in an amount of from about 10 to about 100% by weight of thecontinuous phase, still further from about 20 to about 100% by weight ofthe continuous phase. In further embodiments, the diol is present inabout 25 to about 100% by weight, based on the total weight of thecontinuous phase, preferably from about 30 to about 100% by weight,based on the total weight of the continuous phase, more preferably, fromabout 40 to about 100% by weight, based on the total weight of thecontinuous phase, more preferably, from about 50 to about 100% byweight, based on the total weight of the continuous phase, and, evenmore preferably, about 60 to about 100% by weight, based on the totalweight of this continuous phase. In a further embodiment, the diolcomprises from about 70 to about 100% by weight of the continuous phase,in a further embodiment, about 80 to about 100% by weight of thecontinuous phase, and in still a further embodiment, about 90 to about100% by weight of the continuous phase. In a further embodiment, thediol containing phase consists essentially of the diol component.Suitable diol components for the diol based continuous phase of thesilicone polymer emulsion include, but are not limited to, the diolcomponents described in Section I.

[0076] When the polymer colloid system is a silicone polymer emulsionhaving a water component, the water may be present in an amount of fromabout 10 to about 100% by weight of the continuous phase, morepreferably from about 20 to about 100% by weight of the continuousphase, still preferably, from about 30 to about 100% by weight of thecontinuous phase. In a further preferred embodiment, the water may bepresent at about 40 to about 100% by weight of the continuous phase,more preferably, from about 50 to about 100% by weight of the continuousphase, still preferably from about 60 to about 100% by weight of thecontinuous phase. In further preferred embodiments, the water may bepresent at from about 70 to about 100% by weight of the continuousphase, and, further preferably, at from about 80 to about 100% by weightof the continuous phase and, still preferably, from about 90 to about100% by weight of the continuous phase. In another embodiment, the watermay comprise from about 75 to about 100% by weight of the continuousphase. In yet another embodiment, the continuous phase c onsistsessentially of water.

[0077] The diol component may be present in either the continuous phaseof the silicone polymer emulsion, the condensation polymerizationreaction medium, or both. The diol concentration present in the originalreaction medium may be adjusted to account for the diol concentrationthat may be present in the silicone polymer emulsion. The siliconepolymer emulsion may be introduced into the condensation polymerizationat various stages of the polymerization. For example, in a poly(ethyleneterephthalate) (PET) polymerization, dimethyl terephthalate (DMT),ethylene diol (EG) and catalyst metals are placed in a flask andpolymerized. The silicone polymer emulsion can be added 1) “up front,”i.e., with the other materials at the start; 2) after the other startingmaterials have melted and formed a homogeneous solution; 3) after theDMT and EG have reacted in the first stage and given off MeOH; 4) rightbefore N₂ is turned off and vacuum applied; or 5) sometime during thefinal “polycondensation phase,” or anywhere in between, i.e., during theester exchange phase or polycondensation phase.

[0078] Alternatively, the silicone polymer emulsion may be blended intothe fully or partially formed condensation polymer directly in anextruder at temperatures from about 200 to about 320° C. In thisprocess, since the silicone polymer emulsion is added directly to thecondensation polymer, there is no need to harvest the silicone polymerfrom the emulsion. This provides a more economical process over thoseprocesses discussed in the prior art.

[0079] In one embodiment, the polymer introduced into the condensationpolymerization reaction comprises a glycolyzed polyester, copolyester,polyesteramide or polycarbonate.

[0080] The final blend can be affected by the time at which the siliconepolymer emulsion is added to the condensation polymer. While not wishingto be bound by any mechanism, it is believed that the size and shape ofthe emulsion polymer in the condensation polymer blend can be affectedby the time of the addition. Also, particular chemical interactionbetween silicone polymer and condensation polymers are affected by timeof addition, and, in consequence, will affect the final blendproperties.

[0081] The amount of latex polymer in the condensation polymer/ siliconepolymer blend may comprise a wide range of values. However, it isparticularly preferred that the amount of silicone polymer in the blendis greater than about 5% by weight of the blend. Still further, it ispreferred that the amount of silicone polymer in the condensationpolymer/ silicone polymer blend be from greater than about 5 to about50% by weight of the blend, and, still further preferably, from greaterthan about 5 to about 25 % by weight of the blend.

[0082] In one aspect, the present invention overcomes the necessity ofseparating the silicone polymer from the emulsion prior to addition tothe condensation polymer. Further, since blending takes place during thecondensation polymer formation, there is no need for a polymer/polymerpost blending step that is energy intensive, expensive and often leadsto the reduction of the molecular weight of the condensation polymer.

[0083] In a preferred embodiment, the reaction medium in which thesilicone polymer emulsions of the invention are introduced formspolyesters. The term “polyester,” as used herein, refers to anyunit-type of polyester falling within the scope of the polyester portionof the blend, including, but not limited to, homopolyesters, andcopolyesters (two or more types of acid and/or diol residues ofmonomeric units). The polyesters of the present invention comprise anacid residue and a diol residue. The acid residues of the polyesters ofthe present invention total about 100 mol % and the diol residues of thepolyesters of the present invention total about 100 mol %. It should beunderstood that use of the corresponding derivatives, specifically acidanhydrides, esters and acid chlorides of these acids is includedthroughout the application in the term “acid residue.” In addition tothe acid residue and the diol residue, the polyester may comprise othermodifying residues. These modifying residues include, but are notlimited to, a diamine, which would result in a polyester/amide.

[0084] The polyesters preferably comprise residues of dicarboxylic acidsor esters, including, but not limited to, aromatic dicarboxylic acid orester residues, preferably having from about 8 to about 14 carbon atoms,aliphatic dicarboxylic acid or ester residues, preferably having fromabout 4 to about 12 carbon atoms, or cycloaliphatic dicarboxylic acid orester residues, preferably having from about 8 to about 12 carbon atoms.The acid or ester residue that comprises the acid moiety of thepolyester preferably includes residues of phthalic acid; terephthalicacid, naphthalenedicarboxylic acid, isophthalic acid;cyclohexanediacetic acid; diphenyl 4,4′-dicarboxylic acid; succinicacid; glutaric acid; adipic acid; fumaric acid; azelaic acid;resorcinoldicetic acid; didiolic acid; 4,4′-oxybis(benzoic) acid;biphenyldicarboxylic acid; 1,12-dodecanedicarboxylic acid;4,4′-sulfonyldibenzoic acid; 4,4′-methyldibenzoic acid; trans4,4′-stilbenedicarboxylic acid; 1,2-, 1,3-, and1,4-cyclohexanedicarboxylic acids; or a mixture thereof. The polyestermay be prepared from one or more of the above dicarboxylic acids.

[0085] Preferred examples of dicarboxylic acids or derivatives used toprepare the polyester are terephthalic acid or ester and2,6-napthalenedicarboxylic acid or ester, succinic, isophthalic,glutaric, adipic acid or ester. Other naphthalenedicarboxylic acids ortheir esters may also be used. These include the 1,2-; 1,3-; 1,4-; 1,5-;1,6-; 1,7-; 1,8-; 2,3-; 2,4-; 2,5-; 2,6-; 2,7-; and2,8-naphthalenedicarboxylic acids, or a mixture thereof Even morepreferred is 2,6-napthalenedicarboxylic acid as the modifying acid.

[0086] The diol component of the polyester comprises residues of diolspreferably selected from cycloaliphatic diols preferably having fromabout 6 to about 20 carbon atoms or aliphatic diols preferably havingfrom about 2 to about 20 carbon atoms. Examples of such diols includeethylene diol, diethylene diol, triethylene diol, neopentyl diol, 1,4butanediol, 1,6 hexanediol 1,4-cyclohexanedimethanol, 1,3-propanediol,1,10-decanediol, 2,2,4,4,-tetramethyl-1,3-cyclobutanediol,3-methyl-2,4-pentanediol, 2-methyl-1,4-pentanediol,2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1-1,3-hexanediol,2,2-diethyl-1,3-propanediol, 1,3-hexanediol,1,4-bis(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethylcyclobutaine,2,2-bis-(3-hydroxyethoxyphenyl)propane,2,2-bis-(4-hydroxypropoxyphenyl)propane, or a mixture thereof The diolcomponent is more preferably selected from ethylene diol,1,4-butanediol, neopentyl diol, cyclohexanedimethanol, diethylene diol,or a mixture thereof The diols may be modified with up to about about 50mol % and more preferably up to about 20 mol % of any of the other diolsdisclosed herein.

[0087] It is preferred that the polyesters of the invention areessentially linear. The polyesters may be modified with low levels ofone or more branching agents. A branching agent is herein defined as amolecule that has at least three functional groups that can participatein a polyester forming reaction, such as hydroxyl, carboxylic acid,carboxylic ester, phosphorous-based ester (potentially trifunctional)and anhydride (difunctional).

[0088] Branching agents useful in preparing the polyester of theinvention include, but are not limited to glycerol, pentaerythritol,trimellitic anhydride, pyromellitic dianhydride, tartaric acid, or amixture thereof. If branching agents are used in the condensationpolymerization reaction, a preferred range for the branching agent isfrom about 0.1 to about 2.0 weight %, more preferably from about 0.2 toabout 1.0 weight %, based on the total weight of the polyester.

[0089] Addition of branching agents at low levels does not have asignificant detrimental effect on the physical properties of thepolyester and provides additional melt strength which can be very usefulin film extruding operations. High levels of branching agentsincorporated in the copolyesters result in copolyesters with poorphysical properties, for example, low elongation.

[0090] An agent comprising one or more ion-containing monomers may beadded to increase the melt viscosity of the polyesters. Theion-containing monomers useful in the invention, include, but are notlimited to, alkaline earth metal salts of sulfisophthalic acid or aderivative thereof. The preferred weight percentage for ion-containingmonomers is from about 0.3 to about 5.0 mole %, preferably from about0.3 to about 3.0 mole %. The ion containing monomers also increase themelt viscosity of the polyesters and do not reduce the elongation of thefilms to substantially low levels.

[0091] The homo or copolyesters of the invention are preferably preparedin a reaction carried out using diols and diacids (or diesters oranhydrides) at temperatures from about 150° C. to about 300° C. in thepresence of polycondensation catalysts, including, but not limited to,titanium tetrachloride, titanium tetraisopropoxide, manganese diacetate,antimony oxide, antimony triacetate, dibutyl tin diacetate, zincchloride, or a mixture thereof. The catalysts are typically employed inamounts between about 10 to about 1000 ppm, based on the total weight ofthe reactants. The final stage of the reaction is generally conductedunder high vacuum (about <10 mm of Hg) in order to produce a highmolecular weight polyester.

[0092] The invention also relates to the modification, as discussedherein, of high molecular weight homo or copolyesters prepared by amethod comprising the following steps:

[0093] (I) combining the diols and diacids as described herein, with acatalyst system, wherein the catalyst system comprises Mn, Sb, Ti andother similar metallic species;

[0094] (II) in a first stage, heating said reaction mixture at fromabout 190° C. and about 220° C., at or slightly above atmosphericpressure, and

[0095] (III) in a second stage adding a phosphorous based additive,heating the reaction mixture between about 220° C. and about 290° C.under a reduced pressure of about 0.05 to about 2.00 mm of Hg.

[0096] The polymers of the present invention, e.g., polyesters, arepreferably prepared with one of the above named catalyst systems in thepresence of a phosphorous based additive. The preferred concentration ofcatalyst in the reaction is about 5 to about 220 ppm, with the mostpreferred concentration being about 20 to about 200 ppm. This reactionis best carried out in the two stages as described above.

[0097] In another embodiment of the invention, a polycarbonate may bemodified by introduction of the silicone polymer emulsion into thereaction medium. The polycarbonates that may be modified, include, butare not limited to, homopolymers, copolymers, or a mixture thereof thatare prepared by reacting a dihydric phenol with a carbonate precursor.The dihydric phenols which may be used to produce the carbonate,include, but are not limited to bisphenol-A,(2,2-bis(4-hydroxyphenyl)propane), bis(4-hydroxyphenyl)methane,2,2-bis(4-hydroxy-3-methyl-phenyl)propane, 4,4-bis(4-hydroxyphenylheptane), 2,2-(3,5,3′,5′-tetrachloro-4,4′-dihydroxydiphenyl)propane,2,2-(3,5,3′,5′-tetrabromo-4,4′dihydroxydiphenyl)propane,(3,3′-dichloro-4,4′-dihydroxydiphenyl) methane, or a mixture thereof.Branching agents useful in preparing the polycarbonate of the inventioninclude, but are not limited to glycerol, pentaerythritol, trimelliticanhydride, pyromellitic dianhydride, tartaric acid, or a mixturethereof. If branching agents are used in the condensation polymerizationreaction, a preferred range for the branching agent is from about 0.1 toabout 2.0 weight %, more preferably from about 0.2 to about 1.0 weight%, based on the total weight of the polyester.

[0098] In another embodiment of the invention, the thermoplasticcondensation polymer to be modified by introduction of the siliconepolymer emulsion may comprise a polyurethane. The polyurethane that maybe modified comprises residues of a diol or diols and residues of adi-isocyanante or di-isocyanates. The diol residues of the polyurethanemay be derived from diols including but not limited to,1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol,1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-cyclohexane-1,4-diol,2-methyl-1,4-cyclohexanediol, 2-ethyl-1,4 cyclohexanediol,1,3-cycloheptanediol, 1,4 cycloheptanediol, 2-methyl-1,4cycloheptanediol, 4-methyl-1,3-cycloheptanediol, 1,3-cyclooctanediol,1,4 cyclooctanediol, 1,5 cyclooctanediol, 5-methyl-1,4-cyclooctanediol,5-ethyl-1,4-cyclooctanediol, 5-propyl-1,4 cyclooctanediol,5-butyl,1,4-cyclooctanediol, 5-hexyl-1,4-cyclooctanediol,5-heptyl-1,4-cyclooctanediol, 5-octyl-1,4 cyclooctanediol, 4,4′methylenebis(cyclohexanol), 4,4′-methylenebis(2-methylcyclohexanol),3,3′-methylenebis(cyclohexanol), 4,4′ ethylenebis(cyclohexanol),4,4′propylenebis(cyclohexanol), 4,4′ butylenebis(cyclohexanol), 4,4′isopropylidenebis(cyclohexanol), 4,4′ isobutylenebis(cyclohexanol), 4,4′dihydroxydicyclohexyl, 4,4′ carbonylbis(cyclohexanol),3,3′-carbonylbis(cyclohexanol), 4,4′sulfonylbis(cyclohexanol),4,4′-oxybis(cyclohexanol), or a mixture thereof.

[0099] The polyurethanes of the invention can be prepared using anyknown methods for bringing together, in the presence or absence ofsolvents, polyisocyanates, extenders, and optionally, high molecularweight polyols. This includes manual or mechanical mixing meansincluding casting, reaction extrusion, reaction injection molding andrelated processes. Typical preparative methods useful in the instantinvention are disclosed in U.S. Pat. Nos. 4,376,834 and 4,567,236,incorporated herein in their entireties by this reference, whichdisclosures relate to polyurethane plastic forming ingredients andpreparative procedures.

[0100] The mixing of the reactants may be carried out at ambienttemperature, i.e, at a temperature from about 20° C. to about 25° C. Theresulting mixture is preferably heated to a temperature from about 40°C. to about 130° C., more preferably from about 50° C. to about 100° C.;preferably one or more of the reactants is heated to a temperaturewithin these ranges before admixing.

[0101] A catalyst may optionally be included in the reaction mixturethat is used to prepare the polyurethanes. Any of the catalystsconventionally employed in the art to catalyze the reaction of anisocyanate with a reactive hydrogen containing compound may be used forthis purpose. Suitable catalysts are disclosed in U.S. Pat. No.4,202,957 at column 5, lines 45 to 67, incorporated herein in itsentirety by this reference. The amount of catalyst used is preferablywithin the range of about 0.02 to about 2.0 % by weight, based on thetotal weight of the reactants. In a particular embodiment of theone-shot procedure, the reaction is carried out on a continuous basisusing apparatus and procedures such as that disclosed in U.S. Pat. No.3,642,964, incorporated herein in its entirety by this reference.

[0102] The polyurethanes of this invention include both thermoplasticinjection-moldable and thermoset resins. The thermoplastic resins areobtained by employing substantially difunctional polyisocyanates anddifunctional extenders, and a polyol having a functionality preferablynot exceeding about 4, although polyols having higher functionalitiesmay be employed where the weight proportion used in a low range. As willbe recognized by one skilled in the art, this limit will vary accordingto the nature of the polyol, the molecular weight of the polyol, and theamount of polyol used. In general, the higher the molecular weight ofthe polyol, the higher the functionality which can be employed withoutlosing the thermoplastic properties in the polyurethane product.

[0103] The di-isocyanante residue may be derived from di-isocyanates,including, but not limited to methylenebis(phenyl isocyanate) includingthe 4,4′-isomer, the 2,4′ isomer or a mixture thereof, m-and p-phenylenediisocyanates, chlorophenylene diisocyanates, α, β-xylylenediisocyanate, 2,4-and 2,6-toluene diisocyanates and mixtures of theselatter two isomers, tolidine diisocyanate, hexamethylene diisocyanate,1,5-naphthalene diisocyante, isophorone diisocyanate and the like,cycloaliphatic diisocyanates, such as methylenebis(cyclohexylisocyanate) including the 4,4′ isomer, the 2,4′ isomer or a mixturethereof, and all the geometric isomers thereof including trans/trans,cis/trans, cis/cis or a mixture thereof, cyclohexylene diisocyanantes(1,2, 1,3 or 1,4-), 1-methyl-2,5-cyclohexylene diisocyanate,1-methyl-2,4 cyclohexylene diisocyante, 1-methyl-2,6-cyclohexyldiisocyanate, 4,4′-isopropylidenebis(cyclohexyl isocyanate),4,4′-diisocyanatodicyclohexyl and all geometric isomers, or a mixturethereof. Also included are the modified forms ofmethylenebis(phenylisocyanate). By the latter are meant those forms ofmethylenebis(phenyl isocyanate) which have been treated to render themstable liquids at ambient temperature. Such products include those whichhave been reacted with a minor amount (up to about 0.2 equivalents perequivalent of polyisocyanate) of an aliphatic diol or a mixture ofaliphatic diols such as the modified methylenebis(phenyl isocyanates)described in U.S. Pat. Nos. 3,394,164; 3,644,457; 3,883,571; 4,031,026;4,115,429; 4,118,411; and 4,299,347.

[0104] The modified methylenebis(phenyl isocyanates) also include thosewhich have been treated so as to convert a minor proportion of thediisocyanate to the corresponding carbodiimide which then interacts withfurther diisocyanate to form the aeration-imine groups, the resultingproduct being a stable liquid at ambient temperatures as described, forexample in U.S. Pat. No. 3,384,653. Mixtures of any of the above-namedpolyisocyanates can be employed if desired. Further in the case of thepreparation of those polyurethanes of the invention which are thermoset,it is possible to introduce into the polyisocyanate component employedin the reaction minor amounts (up to about 30 percent by weight) ofpolymethylene polyphenyl polyisocyanates. The latter are mixturescontaining from about 20 to about 90 percent by weight ofmethylenebis(phenyl isocyanate) the remainder of the mixture beingpolymethylene polyphenyl polyisocyanates of functionality higher thanabout 2.0. Such polyisocyanates and methods for their preparation arewell known in the art; see for example, U.S. Pat. Nos. 2,683,730;2,950,263; 3,012,008 and 3,097,191. Branching agents useful in preparingthe polyurethane of the invention include, but are not limited toglycerol, pentaerythritol, trimellitic anhydride, pyromelliticdianhydride, tartaric acid, or a mixture thereof. If branching agentsare used in the condensation polymerization reaction, a preferred rangefor the branching agent is from about 0.1 to about 2.0 weight %, morepreferably from about 0.2 to 1.0 about weight %, based on the totalweight of the polymer.

[0105] The polymers of the invention may be buffered. Buffers can beutilized to control the formation of diethylene glycol, among otheruses. Preferred buffers include, sodium acetate, potassium acetate,lithium acetate, sodium phosphate monobasic, potassium phosphate dibasicand sodium carbonate. Buffering agents are useful to limit the amount ofacidic species which, in turn, causes dehydration of the diols to giveether diol. Accordingly, it can be desirable to limit such acid speciesthrough the use of buffering agents.

[0106] Other ingredients may optionally be added to the compositions ofthe present invention to enhance the performance properties of thecondensation polymer/silicone polymer blend. For example, reinforcingagents, surface lubricants, denesting agents, stabilizers, antioxidants,ultraviolet light absorbing agents, mold release agents, metaldeactivators, colorants such as black iron oxide and carbon black,nucleating agents, phosphate stabilizers, zeolites, fillers, mixturesthereof, and the like, can be included herein. All of these additivesand the uses thereof are well known in the art. Any of these compoundscan be used so long as they do not hinder the present invention fromaccomplishing its objects.

[0107] In a particularly preferred embodiment relating to the additionof reinforcing agents to the compositions of the present invention,glass fibers may be added to the condensation polymer compositions toprovide particular advantages to the resulting compositions. Glassfibers that are preferred in the present invention conventionally havean average standard diameter of greater than about 5 microns, with arange of from about 1 to about 20 microns. The length of the glassfilaments whether or not they are bundled into fibers, and whether thefibers are further bundled into yams, ropes or rovings, and the like,are not critical to this invention. However, for the purpose ofpreparing the present compositions, it is preferable to use filamentousglass in the form of chopped strands of from about 1.5 mm to about 10 mmlong, and, preferably, less than about 6 mm long. In the pellets andmolded articles of the compositions, even shorter lengths will beencountered, because during compounding, considerable fragmentationoccurs. This is, however, desirable because the best properties areexhibited for injection molded articles where the filament lengths arebetween about 0.03 mm and about 1 mm. Especially preferred are glassfibers having an average standard diameter in the range of greater thanabout 5 microns, preferably about 5 microns to about 14 microns, and theaverage filament length dispersed in the molded articles being betweenabout 0.15 and about 0.4 mm. Consequently, glass filaments are disperseduniformly and the molded articles exhibit uniform and balancedmechanical properties, especially surface smoothness.

[0108] The amount of the glass fibers can vary broadly from about 10 toabout 50% by weight, and most preferably about 10 to about 40% byweight, based on the total polymer composition. These glass fibers aretypically conventionally sized with coupling agents, such asaminosilanes and epoxysilanes and titanates, and adhesion promoters suchas epoxies, urethanes, cellulosics, starch, cyanurates, and the like.

[0109] In one embodiment, when the glass fiber is present in the polymermolding composition, the polymer is preferably from about 70 to about85% by weight of the total composition based on the total weightpercentages of the silicone polymers and the condensation polymers,wherein the percentage equals about 100%. Preferably, the polymer in thepolymer molding composition comprises polyester.

[0110] Examples of other reinforcing agents that are useful in additionto glass fibers, include, but are not limited to, carbon fibers, mica,clay, talc, wollastonite, calcium carbonate, or a combination thereof.The polymer compositions of the invention may be reinforced with amixture of glass and other reinforcing agents as described above, suchas mica or talc, and/or with other additives.

[0111] In accordance with the invention herein, the silicone polymeremulsion and glass fibers, as well as other reinforcing agents, may beintroduced into the condensation polymerization at various stages of theprocess. In a particularly preferred embodiment of the invention herein,the glass fibers are added directly to the condensation polymerizationreaction. Since the glass fibers can be sufficiently blended during thisstage, there is no need for a post-blending step, such as extrusion, toincorporate the glass fibers into the compositions. This is particularlyadvantageous to the present invention because a post-blending step isenergy intensive, expensive and may often cause a reduction in themolecular weight of the condensation polymer.

[0112] In a further embodiment, the silicone polymer emulsion maypreferably be introduced into the condensation polymerization at variousstages of a glycolysis reaction. In such a process, a polyester,copolyester, polyesteramide or polycarbonate can be reduced in molecularweight by the additional of a glycol. This reaction takes place veryrapidly at temperatures of from about 200° C. to about 300° C.,preferably at temperatures of about 240° C. to about 280° C.

[0113] The final blend can be affected by the time the silicone polymeris added to the glycolyzed polymer. For example, in the glycolysis ofpoly(ethylene terephthalate) (PET) ,the silicone polymer emulsion can beadded after very little molecular weight reduction (from for example 0.7Ih.V. to 0.6 Ih.V.), e.g., early in the glycolysis reaction, or aftersignificant molecular weight reduction (from for example 0.7 Ih.V. to0.05 Ih.V.), e.g., later in the glycolysis reaction. The final blend canbe affected by the time the silicone polymer emulsion is added to theglycolyzed polymer. While not wishing to be bound by any mechanism, itis believed that the size and shape of the emulsion polymer in thecondensation polymer blend can be affected by the time of the addition.Also, particular chemical interaction between emulsion polymers andcondensation polymers are affected by time of addition, and they, inconsequence, will affect the final blend properties. Such use ofglycolyzed polymers is preferred in some circumstances. An example ofone such circumstance is that the use of glycolyzed polymers in theinvention herein allows a novel use for polymer material that wouldotherwise end up in a waste stream.

[0114] In a preferred embodiment, the diols that may be utilized in theglycolysis reaction include, but are not limited to, any aliphatic orcycloaliphatic diol having from about 2 to about 10 carbon atoms, or amixture thereof. Preferred diols include ethylene diol, 1,3-trimethylenediol, propylene diol, tripropylene diol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol,1,9-nonanediol, neopentyl diol, cis- or trans- cyclohexanedimethanol,cis- or trans- 2,2,4,4-tetramethyl-1,3-cyclobutanediol, diethylene diol,2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propanediol,2-methyl-1,3-pentanediol, or mixtures thereof. More preferred diolsinclude ethylene diol, propylene diol, tripropylene diol,1,4-butanediol, diethylene diol, neopentyl diol, cis and trans-cyclohexanedimethanol or a mixture thereof; even more preferred diolsinclude neopentyl diol, ethylene diol, cis or transcyclohexanedimethanol, 1,4 butanediol, or a mixture thereof.

[0115] In relation to that aspect of the invention pertaining toglycolyzed polymers, the amount of diol in the continuous phase maycomprise from about 25 to about 100% by weight of the continuous phase,from about 50 to about 100% by weight of the ontinuous phase, from about75 to about 100% by weight of the continuous phase, or from about 90 toabout 100% by weight of the continuous phase.

[0116] In another embodiment of the invention, a modified condensationpolymer, including, but not limited to, a thermoplastic elastomer, isproduced from a polymer colloid system comprising a first polymer whichis a silicone polymer. In this embodiment, the both the silicone polymerand the condensation polymer have Tg's of less than about 40° C.Preferably, the condensation polymer has a Tg of less than 0° C. andessentially no crystallinity, even more preferably, the condensationpolymer willl have a Tg of less than −20° C. and will have essentiallyno crystallinity.

[0117] End-use applications for the compositions of the condensationpolymers produced according to the instant invention includeimpact-modified polymers, elastomers, high barrier films and coatings,improved barrier polymers, and polymers having improved mechanicalproperties, such as improved tensile strength, improved elongation atbreak, better weathering properties, and improved flexural strength.Other end-use applications include engineering resins, coatings,containers for barrier applications and molding plastics. In addition,powder coatings may be produced from the modified condensation polymersproduced according to the invention. The polymers produced by thisinvention are useful for thermoplastic engineering resins, elastomers,films, sheets and container plastics.

EXAMPLES

[0118] The following examples are put forth so as to provide those ofordinary skill in the art with a complete disclosure and description ofhow the compositions of matter and methods claimed herein are made andevaluated, and are not intended to limit the scope of what the inventorsregard as their invention. Efforts have been made to insure accuracywith respect to numbers (e.g., amounts, temperature, etc.) but someerrors and deviations should be accounted for. Unless indicatedotherwise, parts are by weight, temperature is in ° C. or is at roomtemperature and pressure is at or near atmospheric.

Example 1 Preparation of Silicone polymer emulsion in Water/EG solution

[0119] To a 65% solids crosslinked polydimethysiloxane emulsion (DowComing Lot 13738-84) was added 1.5 phr of Hitenol HS-20 anionicsurfactant (DKS International). Ethylene glycol was added to theemulsion to dilute the silicone polymer emulsion to 35% solids. Thefinal silicone polymer emulsion contained 35 wt. % PDMS, 46 wt. %ethylene glycol and 19 wt. % water.

Example 2 Incorporation of Crosslinked PDMS into a PET

[0120] The blend was prepared by the following procedure. Dimethylterephthalate (0.5 moles, 97.0 grams), ethylene diol (1.0 moles, 62.0grams), 16.6 grams of the emulsion of Example 1, and catalyst metalswere placed in a 0.5L polymerization reactor under a 1 atmospherenitrogen atmosphere. The mixture was heated with stirring under a slownitrogen purge at 200° C. for 1 hour and then 2 hours at 210° C. Thetemperature was increased to 280° C., the nitrogen flow was stopped andvacuum applied. The polymer was stirred under vacuum (0.1-0.3 Torr) for60 minutes and then stirring was stopped and heat removed.

Example 3

[0121] A 65% solids crosslinked polydimethysiloxane emulsion (Dow ComingLot 13738-84) was was diluted to 50% solids with distilled water. Tothis was added 1.5 phr of FES 77 surfactant (Henkle Corp). Ethyleneglycol was added to the emulsion to dilute the silicone polymer emulsionto 35% solids. The final silicone polymer emulsion contained 35 wt. %PDMS, 36.5 wt. % ethylene glycol and 28.5 wt. % water.

Example 4

[0122] The blend was prepared by the following procedure. Dimethylterephthalate (0.5 moles, 97.0 grams), ethylene glycol (1.0 mole, 62.0grams), 14.3 grams silicone polymer emulsion from Example 3 (30% solids)and catalyst metals were placed in a 0.5L polymerization reactor under a1 atmosphere nitrogen atmosphere. The mixture was heated with stirringunder a slow nitrogen purge at 200° C. for 1 hour and then 210° C. fortwo hours. The temperature was increased to 280° C. and then nitrogenwas shut off and vacuum applied. After 10 minutes of vacuum (0.35 Torrachieved), the vacuum was removed, nitrogen was bled in to increase thepressure to atmospheric pressure and 56.6 grams of the silicone polymeremulsion from Example 2 was added with a 125 mL pressure-equalizingfunnel over a 10 minute period. Again, nitrogen flow was shut off and avacuum applied. Pressure of 0.3-0.5 Torr was maintained for 1 hour asthe viscous melt was stirred. Heat was removed and the polymer wasallowed to cool and then ground. A tough opaque white film wasmelt-pressed at 240° C. for 15 seconds. The Ih.V. was 1.1 dL/g, the Tgwas −25° C. (2nd cycle), the Tm was 248.2° C. (2nd cycle). TEM showedthat the rubber particles were 0.4 microns in size in the polyesterblend.

[0123] The invention has been described in detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be effected without departing fromthe scope and spirit of the invention.

What is claimed is:
 1. A silicone polymer emulsion comprising: a. a silicone polymer; b. a surfactant; and c. a liquid continuous phase comprising a diol, wherein the diol comprises from about 25 to about 100% by weight of the continuous phase.
 2. The silicone polymer emulsion of claim 1, wherein the diol comprises ethylene diol, 1,3-trimethylene diol, 1,3-propylene diol, tripropylene diol, 1,4-butanediol, 1,5-pentanediol, 1,6 hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl diol, cis- or trans cyclohexanedimethanol, cis or trans 2,2,4,4-tetramethyl-1,3 cyclobutanediol, diethylene diol, or a mixture thereof.
 3. The silicone polymer emulsion of claim 1, wherein the continuous phase comprises water.
 4. The silicone polymer emulsion of claim 1, wherein the continuous phase comprises from about 1 to about 75% by weight water.
 5. The silicone polymer emulsion of claim 1, wherein the surfactant comprises alkali metal, ammonium salts of alkyl, aryl or alkylaryl sulfonates, sulfates, phosphates, alkyl and alkylaryl polydiol ethers, ethoxylation products of lauryl, oleyl and stearyl alcohols, alkyl phenol glycol ethers, ethoxylation products of octyl or nonylphenol, or a mixture thereof.
 6. The silicone polymer emulsion of claim 1, wherein the silicone polymer comprises homo or copolymers of polydimethylsiloxane, wherein the copolymers comprise aminopropyl, vinyl, mercaptopropyl, phenylmethyl, epoxy or amino-ethylaminopropyl functionalities. 